JPWO2020071339A1 - Substrate manufacturing method, composition and polymer - Google Patents

Abstract

An object of the present invention is to provide a method for producing a substrate, a composition, and a polymer capable of easily producing a substrate having a metal-containing layer on the surface of the metal substrate. The present invention is a method for manufacturing a substrate including a step of coating a composition on a metal substrate and a step of forming a metal-containing layer on at least a part of the coating film formed by the coating step. The composition contains a polymer having a first-terminal structure and a second-terminal structure on the same molecule as the solvent, and the first-terminal structure and the second-terminal structure are represented by the following formulas (1), respectively. It is characterized in that it is at least one selected from the group consisting of the above-mentioned structure and the structure represented by the following formula (2). In the following formula (1), A1 is a monovalent group containing a functional group capable of chemically bonding with a metal atom. In the following formula (2), L2 is -S-, -NR- or -NA22-. A2 and A22 are monovalent groups containing a functional group capable of chemically bonding with a metal atom. [Selection diagram] None

Description

The present invention relates to a method for producing a substrate, a composition and a polymer.

When manufacturing a semiconductor device or the like, various layers are formed on the surface of a metal substrate. As a method for forming such a layer, for example, a method for selectively modifying a substrate having a fine region on the surface layer has been studied. This modification method requires a material capable of easily modifying the surface region, and various methods have been studied (Japanese Patent Laid-Open No. 2016-25315, JP-A-2003-76036, ACS Nano, JP. See 9, 9, 8710, 2015, ACS Nano, 9, 9, 8651, 2015, Science, 318, 426, 2007 and Langmuir, 21, 8234, 2005).

Japanese Unexamined Patent Publication No. 2016-25315 Japanese Unexamined Patent Publication No. 2003-76036

ACS Nano, 9, 9, 8710, 2015 ACS Nano, 9, 9, 8651, 2015 Science, 318, 426, 2007 Langmuir, 21, 8234, 2005

Recently, it has been required to form a metal-containing layer containing a metal atom as a layer to be formed on the surface of a metal substrate. However, with the above-mentioned conventional materials, it is difficult to use for forming a metal-containing layer, and a method capable of easily forming a metal-containing layer is required.

The present invention has been made based on the above circumstances, and an object of the present invention is a method and composition for producing a substrate capable of easily producing a substrate having a metal-containing layer formed on the surface of the metal substrate. And to provide a polymer.

（式（１）中、Ｌ^１は、炭素数１〜２０の３価の基である。Ａ^１は、金属原子と化学結合可能な官能基を含む１価の基である。Ｘは、水素原子、炭素数１〜２０の１価の有機基、−ＳＨ又は−Ｓ−Ａ^１１である。Ａ^１１は、金属原子と化学結合可能な官能基を含む１価の基である。ｎは、（−Ｌ^１（−Ａ^１）−）_ｎで表されるブロックを構成する構造単位の数を示し、２以上の整数である。複数のＡ^１は同一でも異なっていてもよく、Ａ^１及びＡ^１１は、同一でも異なっていてもよい。＊は、上記重合体における上記式（１）で表される構造以外の部分に結合する部位を示す。
式（２）中、Ｌ^２は、−Ｓ−、−ＮＲ−又は−ＮＡ^２２−である。Ａ^２及びＡ^２２は、それぞれ独立して、金属原子と化学結合可能な官能基を含む１価の基である。Ｒは、水素原子又は炭素数１〜２０の１価の炭化水素基である。ｍは、０又は１である。＊は、上記重合体における上記式（２）で表される構造以外の部分に結合する部位を示す。）The invention made to solve the above problems is a step of coating a composition on at least one surface of a metal substrate and a surface of a coating film formed by the coating step on the opposite side of the metal substrate. A method for producing a substrate comprising a step of forming a metal-containing layer in at least a part of the above, wherein the composition contains a polymer having a first-terminal structure and a second-terminal structure on the same molecule and a solvent. The first terminal structure and the second terminal structure are at least one selected from the group consisting of the structure represented by the following formula (1) and the structure represented by the following formula (2). do.

(In the formula (1), L ¹ is a trivalent group having 1 to 20 carbon atoms. A ¹ is a monovalent group containing a functional group that can be chemically bonded to a metal atom. X is hydrogen. atom, a monovalent organic group having 1 to 20 carbon atoms, ^{.A 11} is -SH or ^{-S-a 11} is a monovalent group containing a metal atom capable of chemically bonding functional groups .n is (-L ¹ (-A ¹ )-) _{Indicates the number of structural units constituting the block represented by n} , which is an integer of 2 or more. A plurality of A ^1s may be the same or different, and A ¹ and A ¹¹ may be the same or different. * Indicates a site of the polymer that binds to a portion other than the structure represented by the above formula (1).
Wherein ^{(2), L} 2 is, -S -, - NR- or ^{-NA 22} - a. A ² and A ²² are monovalent groups each independently containing a functional group capable of chemically bonding with a metal atom. R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. m is 0 or 1. * Indicates a site that binds to a portion of the polymer other than the structure represented by the above formula (2). )

Another invention made to solve the above problems is a composition used in a method for producing a substrate including a metal substrate and a metal-containing layer formed on at least one surface side of the metal substrate, which are the same. A polymer having a first-terminal structure and a second-terminal structure and a solvent are contained on the molecule, and the first-terminal structure and the second-terminal structure are the structure represented by the above formula (1) and the above formula (2). ) Is at least one selected from the group consisting of the structures represented by).

Yet another invention made to solve the above problem has a first terminal structure and a second terminal structure on the same molecule, and the first terminal structure and the second terminal structure are represented by the above formula (1). It is a polymer which is at least one selected from the group consisting of the structure described above and the structure represented by the above formula (2).

Here, the "metal substrate" refers to a substrate containing a metal atom in at least a part of the surface layer.

According to the method for manufacturing a substrate of the present invention, it is possible to easily manufacture a substrate having a metal-containing layer formed on the surface of the metal substrate. The composition of the present invention can be suitably used in the method for producing the substrate. The polymer of the present invention can be suitably used as a polymer component of the composition. Therefore, these can be suitably used for processing processes of semiconductor devices, which are expected to be further miniaturized in the future.

Hereinafter, embodiments of the method for manufacturing the substrate will be described in detail.

<Manufacturing method of substrate>
The method for manufacturing the substrate is a step of applying a composition (hereinafter, also referred to as “composition (S)”) to at least one surface of a metal substrate (hereinafter, also referred to as “metal substrate (X)”) (hereinafter, also referred to as “composition (S)”). , Also referred to as "coating process") and the surface of the coating film formed by the coating process (hereinafter, also referred to as "coating film (P)") on the side opposite to the metal substrate (X). At least a part thereof includes a step of forming a metal-containing layer (hereinafter, also referred to as “metal-containing layer (Y)”) (hereinafter, also referred to as “metal-containing layer forming step”). The method for producing the substrate is as follows, as the composition (S), on the same molecule, a first terminal structure (hereinafter, also referred to as “terminal structure (I)”) and a second terminal structure (hereinafter, “terminal structure (II)). (Hereinafter, also referred to as “[A] polymer”) and a solvent (hereinafter, also referred to as “[B] solvent”), and the terminal structure (I) and the terminal structure (hereinafter, also referred to as “[B] solvent”). II) is derived from the structure represented by the following formula (1) (hereinafter, also referred to as "structure (1)") and the structure represented by the following formula (2) (hereinafter, also referred to as "structure (2)"). At least one selected from the group is used.

In the above formula (1), L ¹ is a trivalent group having 1 to 20 carbon atoms. A ¹ is a monovalent group containing a functional group capable of chemically bonding with a metal atom. X is a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, -SH or -SA ¹¹ . A ¹¹ is a monovalent group containing a functional group capable of chemically bonding with a metal atom. n indicates the number of structural units constituting the block represented by ^{(-L 1} (-A ¹ )-) _{n, and is an integer of 2 or more.} A plurality of A ^1s may be the same or different, and A ¹ and A ¹¹ may be the same or different. * Indicates a site of the polymer [A] that binds to a portion other than the structure represented by the above formula (1).

In the formula ^{(2), L} 2 is, -S -, - NR- or ^{-NA 22} - a. A ² and A ²² are monovalent groups each independently containing a functional group capable of chemically bonding with a metal atom. R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. m is 0 or 1. * Indicates a site of the polymer [A] that binds to a portion other than the structure represented by the above formula (2).

According to the method for manufacturing the substrate, a substrate including the metal substrate (X) and the metal-containing layer (Y) formed on at least one surface side of the metal substrate (X) is manufactured. According to the method for producing the substrate, each of the above steps is provided, and the composition (S) contains the polymer [A] to easily produce a substrate having a metal-containing layer formed on the surface of the metal substrate. be able to. The reason why the above-mentioned effect is obtained by providing the above-mentioned configuration in the manufacturing method of the substrate is not always clear, but it can be inferred as follows, for example. That is, the [A] polymer has a terminal structure containing a functional group capable of chemically bonding with a metal atom at both ends. By coating the surface of the metal substrate with the composition (S), the [A] polymer has a functional group capable of chemically bonding with a metal atom in one of the terminal structures and chemically with the metal atom in the metal substrate (X). By being bonded, it is arranged on the surface of the metal substrate (X). A metal-containing layer can be easily formed by using a functional group capable of chemically bonding with a metal atom in the other terminal structure of the arranged [A] polymer. As described above, according to the method for manufacturing the substrate, it is possible to easily manufacture the substrate in which the metal-containing layer is formed on the surface of the metal substrate.
Hereinafter, each step will be described.

<Coating process>
In this step, the composition (S) is applied to at least one surface of the metal substrate (X).

The metal atom (first metal atom, hereinafter also referred to as "metal atom (A)") contained in the metal substrate (X) is not particularly limited as long as it is an atom of a metal element. Silicon and boron are not included in the metal atom (A). Examples of the metal atom (A) include copper, iron, zinc, cobalt, aluminum, tin, tungsten, zirconium, titanium, tantalum, germanium, molybdenum, ruthenium, gold, silver, platinum, palladium, nickel and the like. Of these, copper or cobalt is preferred.

Examples of the form containing the metal atom (A) in the metal substrate (X) include simple substances of metals, alloys, metal nitrides, metal oxides, VDD and the like.

Examples of the simple substance of the metal include a simple substance of a metal such as copper, cobalt, aluminum, and tungsten.
Examples of the alloy include nickel-copper alloy, cobalt-nickel alloy, gold-silver alloy and the like.
Examples of the metal nitride include titanium nitride, tantalum nitride, iron nitride, aluminum nitride and the like.
Examples of the metal oxide include tantalum oxide, aluminum oxide, iron oxide, copper oxide and the like.
Examples of the silicide include iron silicide, molybdenum silicide and the like.
Among these, a simple substance of metal is preferable, and copper or cobalt is more preferable.

In the surface layer of the metal substrate (X), in addition to the region containing the metal atom (A) (hereinafter, also referred to as “region (I)”), for example, substantially non-metal atom (hereinafter, “non-metal atom (C)”). ) ”) (Hereinafter, also referred to as“ region (II) ”) and the like. Examples of the non-metal atom (C) include silicon, boron, carbon, oxygen, nitrogen, hydrogen and the like.

Examples of the form containing the non-metal atom (C) in the region (II) include non-metal simple substances, non-metal oxides, non-metal nitrides, non-metal oxynitrides, non-metal carbide oxides and the like.

Examples of the non-metal simple substance include non-metal simple substances such as silicon, boron, and carbon.
Examples of the non-metal oxide include _{hydrolyzable condensates of hydrolyzable silanes such as tetraalkoxysilanes such as silicon dioxide (SiO 2} ) and tetraethoxysilane (TEOS), and boron oxide.
Examples of the non-metal nitride include silicon nitride and boron nitride.
Examples of the non-metal nitrogen oxide include silicon nitrogen oxide and boron nitrogen oxide.
Examples of the non-metal carbonized oxide include silicon carbide (SiOC) and the like.

When the metal substrate (X) has the region (I) and the region (II), the existing shape of the region (I) and the region (II) on the surface layer of the metal substrate (X) is not particularly limited, and is, for example, in a plan view. Plane-like, dot-like, striped-like, and the like can be mentioned. The sizes of the region (I) and the region (II) are not particularly limited, and can be appropriately set to a desired size.

The shape of the metal substrate (X) is not particularly limited, and can be appropriately formed into a desired shape such as a plate shape (board) or a spherical shape.

The surface of the metal substrate (X) is preferably washed with, for example, an aqueous solution of oxalic acid of about 5% by mass.

Examples of the coating method of the composition (S) include a spin coating method and the like. It may be heated after the above coating. The lower limit of the heating temperature is preferably 50 ° C., more preferably 80 ° C. The upper limit of the temperature is preferably 200 ° C., more preferably 150 ° C. As the lower limit of the heating time, 10 seconds is preferable, and 30 seconds is more preferable. The upper limit of the time is preferably 1 hour, more preferably 10 minutes. After the heating, it is preferable to wash and remove the [A] polymer that is not chemically bonded to the surface of the metal substrate (X) with a solvent such as propylene glycol monomethyl ether acetate (PGMEA). In this way, the coating film (P) is formed.

The lower limit of the contact angle of water on the surface of the coating film (P) is preferably 70 °, more preferably 80 °, and even more preferably 85 °. The upper limit of the contact angle is, for example, 100 °.

Hereinafter, the composition (S) will be described.

<Composition (S)>
The composition (S) is used in a method for producing a substrate including a metal substrate (X) and a metal-containing layer (Y) formed on at least one surface side of the metal substrate (X). The composition (S) contains the [A] polymer and the [B] solvent. The composition (S) may contain other components in addition to the [A] polymer and the [B] solvent as long as the effects of the present invention are not impaired. Hereinafter, each component will be described.

[[A] Polymer]
[A] The polymer is a polymer having a terminal structure (I) and a terminal structure (II) on the same molecule. The [A] polymer is usually a structural unit derived from a monomer (hereinafter, also referred to as “monomer (a)”) between the terminal structure (I) and the terminal structure (II) (hereinafter, “A”. It also has a structural unit (A).

(End structure)
The terminal structure (I) and the terminal structure (II) are at least one selected from the group consisting of the structure (1) and the structure (2).

^{A 1} in the formula (1) in the structure (1), ^{A 11} When X in the above formula (1) is ^{-S-A 11, A} 2 in the formula (2) in the structure (2), and the formula (2) ^{L 2} is ^{-NA 22} - ^{a 22} when it is a metal atom capable of chemically bonding functional groups (hereinafter, also referred to as "functional group (M)") a monovalent group including (Hereinafter, also referred to as "group (I)").

The functional group (M) is a functional group capable of chemically bonding with a metal atom. Examples of the metal atom that can be chemically bonded to the functional group (M) include a metal atom (A) contained in the metal substrate (X) and a metal atom (second metal atom, hereinafter referred to as “2nd metal atom” contained in the metal-containing layer (Y) described later. (Also referred to as "metal atom (B)") and the like. Examples of the chemical bond between the metal atom and the functional group (M) include a covalent bond, an ionic bond, and a coordination bond. Among these, a coordination bond is preferable from the viewpoint that the bonding force between the metal atom and the functional group (M) is larger.

Examples of the functional group (M) include a phosphoric acid group, a nitrile group, a carboxy group, an ester group, a hydroxy group and the like. The phosphate group refers to a group represented by -PO (OH) _2. The ester group means a group represented by -COOR (R is a monovalent organic group).

Examples of the group (I) include a group represented by the following formula (i) (hereinafter, also referred to as “group (i)”).

In the above formula (i), E is a single bond, -COO-, -CO-, -O-, -NH-, -NHCO- or -CONH-. Q is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. R ¹ is a monovalent functional group (M). p is an integer from 0 to 10. However, when p is 1 or more, Q is not a single bond. * Indicates a site that binds to ^{L 1} in the above formula (1).

As E, a single bond or -COO- is preferable, and a single bond is more preferable.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by Q include an alkanediyl group, a cycloalkanediyl group, an arenediyl group, and an allenediyl alkanediyl group.

As Q, a single bond or an alkanediyl group is preferable, and a single bond is more preferable.

Examples of the monovalent functional group (M) represented by R ¹ include monovalent groups among the groups exemplified as the functional group (M).

As p, 0 to 2, 0 or 1, is more preferable, and 0 is even more preferable.

As the group (i), a phosphate group, a cyanoalkyl group, a carboxy group, a carboxyalkyl group, an ester group, a hydroxy group or a hydroxyalkyl group is preferable. Examples of the cyanoalkyl group include a 1-cyano-1-methylethyl group. Examples of the carboxyalkyl group include a 2-carboxyethyl group and the like. Examples of the ester group include a methoxycarbonyl group and the like. Examples of the hydroxyalkyl group include a 2-hydroxyethyl group and the like.

A phosphoric acid group is preferable as ^{A 1} in the above formula (1). ^{Further, as A 2} in the above formula (2), at least one selected from the group consisting of a nitrile group, a carboxy group, an ester group and a hydroxy group is preferable.

^{L 1} in the above formula (1) is a group constituting a part of the main chain of the [A] polymer. The "main chain" refers to the longest atomic chain of the [A] polymer. Examples of the trivalent group having 1 to 20 carbon atoms represented by L ¹ include a group derived from a carbon-carbon double bond-containing group, a group derived from an oxyalkylene group, and the like.

Examples of the monovalent organic group having 1 to 20 carbon atoms represented by X in the above formula (1) include a monovalent hydrocarbon group having 1 to 20 carbon atoms and 2 carbon-carbon groups of the hydrocarbon group. Examples include a group containing a valent heteroatom-containing group, a group in which a part or all of the hydrogen atoms of the above-mentioned hydrocarbon group and the above-mentioned divalent heteroatom-containing group are substituted with a monovalent heteroatom-containing group, and the like. Be done. "Organic group" means a group containing at least one carbon atom.

The "hydrocarbon group" includes a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. This "hydrocarbon group" may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The "chain hydrocarbon group" refers to a hydrocarbon group composed only of a chain structure without containing a cyclic structure, and includes both a linear hydrocarbon group and a branched hydrocarbon group. The "alicyclic hydrocarbon group" refers to a hydrocarbon group containing only an alicyclic structure as a ring structure and not containing an aromatic ring structure, and refers to a monocyclic alicyclic hydrocarbon group and a polycyclic alicyclic group. Contains both hydrocarbon groups. However, it does not have to be composed only of an alicyclic structure, and a chain structure may be included as a part thereof. The "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it does not have to be composed only of an aromatic ring structure, and a chain structure or an alicyclic structure may be included as a part thereof. The "ring member number" refers to the number of atoms constituting the alicyclic structure, the aromatic ring structure, the aliphatic heterocyclic structure and the aromatic heterocyclic structure, and in the case of a polycycle, the number of atoms constituting the polycycle. To say.

The monovalent hydrocarbon groups having 1 to 20 carbon atoms include monovalent chain hydrocarbon groups having 1 to 20 carbon atoms, monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms. Examples thereof include 20 monovalent aromatic hydrocarbon groups.

Examples of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, and an i-propyl group;
Alkenyl groups such as ethenyl group, propenyl group, butenyl group;
Examples thereof include an alkynyl group such as an ethynyl group, a propynyl group and a butynyl group.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a monocyclic alicyclic saturated hydrocarbon group such as a cyclopentyl group and a cyclohexyl group;
Monocyclic alicyclic unsaturated hydrocarbon groups such as cyclopentenyl group and cyclohexenyl group;
Polycyclic alicyclic saturated hydrocarbon groups such as norbornyl group, adamantyl group, and tricyclodecyl group;
Examples thereof include polycyclic alicyclic unsaturated hydrocarbon groups such as norbornenyl group and tricyclodecenyl group.

Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include an aryl group such as a phenyl group, a tolyl group, a xsilyl group, a naphthyl group and an anthryl group;
Examples thereof include an aralkyl group such as a benzyl group, a phenethyl group, a naphthylmethyl group and an anthrylmethyl group.

Examples of the hetero atom constituting the divalent or monovalent hetero atom-containing group include an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom, a halogen atom and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the divalent heteroatom-containing group include -O-, -CO-, -S-, -CS-, and a group in which two or more of these are combined. Of these, -O- is preferable.

Examples of the monovalent heteroatom-containing group include a halogen atom and the like.

As X in the above formula (1), a hydrogen atom or -SH is preferable, and a hydrogen atom is more preferable.

As the upper limit of n in the above formula (1), 10 is preferable, and 5 is more preferable.

^{The lower limit of the content ratio of the structural unit represented by (-L 1} (-A ¹ )-) in the above formula (1) is 0.1 with respect to all the structural units constituting the [A] polymer. Mol% is preferred, 0.5 mol% is more preferred, 1 mol% is even more preferred, and 2 mol% is particularly preferred. The upper limit of the content ratio is preferably 30 mol%, more preferably 20 mol%, further preferably 10 mol%, and particularly preferably 7 mol%.

^{Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R in −NR− of L 2} of the above formula (2) include those having 1 to 20 carbon atoms exemplified as X in the above formula (1). Examples thereof include groups similar to monovalent hydrocarbon groups. As L ² , -S- or -NR- is preferable, and -NH- is preferable among -NR-.

As m, 0 is preferable.

Examples of the terminal structure (I) include a structure containing a block derived from vinyl phosphate, a structure containing a block derived from (meth) acrylic acid, a structure containing a block derived from ( _{-CH 2-} CH (OH)-), and the like. Can be mentioned.

Examples of the terminal structure (II) include a cyanoalkyl group, a carboxyalkyl group, and a hydroxyalkyl group.

It is preferable that the functional group (M) in the terminal structure (I) and the functional group (M) in the terminal structure (II) are different from each other. When the functional group (M) is different between the terminal structure (I) and the terminal structure (II), a metal-containing layer (Y) containing a metal atom different from the metal atom (A) of the metal substrate (X) is formed. It will be easier to do.

It is preferable that the terminal structure (I) is the structure (1) and the terminal structure (II) is the structure (2). When each of the terminal structures has the above-mentioned structure, it becomes easier to form a metal-containing layer (Y) containing a metal atom different from the metal atom (A) of the metal substrate (X).

(Structural unit (A))
The structural unit (A) is a structural unit derived from the monomer (a). [A] The polymer usually has a structural unit (A) between the terminal structure (I) and the terminal structure (II).

Examples of the monomer (a) that gives the structural unit (A) include a vinyl aromatic compound, (meth) acrylic acid or (meth) acrylic acid ester, substituted or unsubstituted ethylene, and a polymerizable compound having a crosslinkable group. And so on. The "crosslinkable group" refers to a group that forms a crosslinked structure by a reaction under heating conditions, active energy ray irradiation conditions, acidic conditions, and the like. As the monomer (a), one kind or two or more kinds of these compounds may be used.

Examples of vinyl aromatic compounds include styrene;
α-Methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4,6-trimethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, o- Hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, m-chloromethylstyrene, p-chloromethylstyrene, p-chlorostyrene, p-bromostyrene, p-iodostyrene, p-nitrostyrene, p-cyanostyrene, etc. Substituted styrene;
Vinyl naphthalene;
Substituted vinylnaphthalene such as vinylmethylnaphthalene and vinylchloronaphthalene;
Vinyl anthracene;
Substituted vinyl anthracene such as vinyl methyl anthracene and vinyl chloro anthracene;
Vinyl pyrene;
Examples thereof include substituted vinylpyrene such as vinylmethylpyrene and vinylchloropyrene.

Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. ;
Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 2-ethyladamantyl (meth) acrylate, 2- (adamantane-1-yl) propyl (meth) acrylate, etc. (Meta) acrylic acid cycloalkyl ester;
(Meta) acrylic acid substituted alkyl esters such as 2-hydroxyethyl (meth) acrylic acid, 3-hydroxyadamantyl (meth) acrylic acid, 3-glycidylpropyl (meth) acrylic acid, 3-trimethylsilylpropyl (meth) acrylic acid, etc. Can be mentioned.

Examples of the substituted ethylene include alkenes such as propene, butene, and pentane;
Vinyl cycloalkanes such as vinyl cyclopentane and vinyl cyclohexane;
Cycloalkenes such as cyclopentene and cyclohexene;
Examples thereof include vinyl phosphate, 4-hydroxy-1-butene, vinyl glycidyl ether, vinyl trimethylsilyl ether and the like.

Examples of the crosslinkable group in the polymerizable compound having a crosslinkable group include a polymerizable carbon-carbon double bond-containing group such as a vinyl group, a vinyloxy group, an allyl group, a (meth) acryloyl group, and a styryl group;
Cyclic ether groups such as oxylanyl group, oxylanyloxy group, oxetanyl group, oxetanyloxy group;
An aryl group in which a cyclobutane ring is fused, such as a phenyl group in which a cyclobutane ring is fused and a naphthyl group in which a cyclobutane ring is fused;
An aryl group to which an acyl group such as an acetoxyphenyl group or a t-butoxyphenyl group or an aromatic hydroxy group protected by a thermodispersible group is bonded;
An aryl group to which an acyl group such as an acetoxymethylphenyl group or a methoxymethylphenyl group or a methylol group (-CH ₂ OH) protected by a thermodispersible group is bonded;
Examples thereof include an aryl group to which _{a substituted or unsubstituted sulfanylmethyl group (-CH 2} SH) such as a sulfanylmethylphenyl group and a methylsulfanylmethylphenyl group is bonded.

Aryl groups in which the cyclobutane ring is fused form a covalent bond under heating conditions.

The "acyl group" is a group obtained by removing OH from a carboxylic acid and refers to a group that protects by substituting a hydrogen atom of an aromatic hydroxy group or a methylol group. The "thermally dissociable group" is a group that replaces a hydrogen atom of an aromatic hydroxy group, a methylol group, or a sulfanylmethyl group, and means a group that dissociates by heating.

Examples of the acyl group in the aryl group to which the protected aromatic hydroxy group, methylol group or sulfanylmethyl group is bonded include formyl group, acetyl group, propionyl group, butyryl group, benzoyl group and the like.

Examples of the thermally dissociable group in the aryl group to which the protected aromatic hydroxy group is bonded include a tertiary alkyl group such as a t-butyl group and a t-amyl group. Examples of the thermally dissociable group in the aryl group to which the protected methylol group or the sulfanylmethyl group is bonded include an alkyl group such as a methyl group, an ethyl group and a propyl group.

Examples of the polymerizable compound containing a crosslinkable group include a vinyl compound having a crosslinkable group such as styrene having a crosslinkable group, and a (meth) acrylic compound having a crosslinkable group.

As the structural unit (A), a structural unit derived from hydrocarbon group-substituted or unsubstituted styrene (hereinafter, also referred to as “structural unit (A-1)”) is preferable. When the structural unit (A) is a structural unit (A-1) that does not contain a functional group (M), the metal-containing layer (Y) can be formed more effectively.

Examples of the monomer (a) that gives the structural unit (A-1) include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2, 4,6-trimethylstyrene, etc.
Further, among the polymerizable compounds having a crosslinkable group, o-vinylstyrene, m-vinylstyrene, p-vinylstyrene, 4-vinylbenzocyclobutene and the like can be mentioned.

The structural unit (A) is selected from the group consisting of a structural unit derived from a vinyl aromatic compound, a structural unit derived from (meth) acrylic acid or (meth) acrylic acid ester, and a structural unit derived from substituted or unsubstituted ethylene. When at least one of these structural units is contained, the lower limit of the total content of these structural units in the structural unit (A) is preferably 50 mol%, more preferably 80 mol%, further preferably 90 mol%, and 95 mol. % Is particularly preferable. The total content ratio may be 100 mol%.

When the structural unit (A) contains a structural unit derived from a polymerizable compound having a crosslinkable group, the lower limit of the content ratio of these structural units in the structural unit (A) is preferably 0.1 mol%. 0.5 mol% is more preferable, 1 mol% is more preferable, 2 mol% is particularly preferable, and the upper limit of the content ratio is preferably 30 mol%, more preferably 20 mol%, still more preferably 10 mol%. 5 mol% is particularly preferred.

[A] As the lower limit of the number average molecular weight (Mn) of the polymer, 1,000 is preferable, 2,000 is more preferable, 3,000 is further preferable, and 4,000 is particularly preferable. As the upper limit of Mn, 100,000 is preferable, 50,000 is more preferable, 30,000 is further preferable, and 10,000 is particularly preferable. By setting the Mn of the polymer in the above range, the metal-containing layer (Y) can be formed more effectively.

[A] As the upper limit of the ratio (dispersity) of the weight average molecular weight (Mw) of the polymer to Mn, 5 is preferable, 2 is more preferable, 1.5 is more preferable, and 1.3 is particularly preferable. The lower limit of the ratio is usually 1, preferably 1.05.

The lower limit of the content of the polymer [A] is preferably 60% by mass, more preferably 80% by mass, further preferably 90% by mass, and 95% by mass with respect to the total solid content in the composition (S). Especially preferable. The content may be 100% by mass. The “total solid content” refers to all the components of the composition (S) other than the [B] solvent.

(Method for synthesizing polymer)
[A] In the case of a polymer having a terminal structure (I) having a structure (1) and a terminal structure (II) having a structure (2), for example, a structure such as azobisisobutyronitrile (AIBN). Using the polymerization initiator that gives (2), first polymerize the monomer (a) that gives the structural unit (A) such as styrene, tert-butylstyrene, 4-vinylbenzocyclobutene, and then vinyl phosphate and the like. It can be synthesized by polymerizing the monomer giving the structure (1) of (1) to form a block.

In the above polymerization, trithiocarbonate compounds such as 2-cyano-2-propyldodecyltrithiocarbonate and dibenzyltrithiocarbonate, dithiocarbamate compounds such as cyanomethyl-N-methyl-N-phenyldithiocarbamate, 2- RAFT polymerization may be carried out using a dithiobenzoate compound such as cyano-2-propylbenzodithionate or a xanthate compound such as xanthate-O-ethyl-S-cyanomethyl as a RAFT agent. Further, a radical generator such as AIBN and a thiol compound such as tert-dodecanethiol are added to the polymer obtained by RAFT polymerization using the above RAFT agent, and a terminal separation reaction such as a trithiocarbonate terminal is carried out. Then, the end of the main chain of the [A] polymer can be a hydrogen atom or the like. In this separation reaction, it is preferable to use a protonal solvent such as alcohol as a proton supply source in addition to the radical generator and the thiol compound.

A polymer [A] other than the above-mentioned polymer can also be synthesized by a known method.

[[B] Solvent]
The solvent [B] is not particularly limited as long as it is a solvent capable of dissolving or dispersing at least the polymer [A] and other components.

Examples of the solvent [B] include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents and the like.

Examples of the alcohol solvent include monoalcohol solvents such as methanol and ethanol;
Polyhydric alcohol solvents such as ethylene glycol and 1,2-propylene glycol;
Polyhydric alcohol partial ether-based solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether;
Examples thereof include lactic acid ester-based solvents such as methyl lactate, ethyl lactate, n-butyl lactate, and n-amyl lactate.

Examples of the ether solvent include dialkyl ether solvents such as diethyl ether;
Cyclic ether solvent such as tetrahydrofuran;
Examples thereof include an aromatic ring-containing ether solvent such as anisole.

Examples of the ketone solvent include chain ketone solvents such as butanone and methyl-iso-butyl ketone;
Cyclic ketone solvents such as cyclopentanone and cyclohexanone can be mentioned.

Examples of the amide solvent include cyclic amide solvents such as N, N'-dimethylimidazolidinone and N-methylpyrrolidone;
Examples thereof include chain amide solvents such as N-methylformamide and N, N-dimethylformamide.

Examples of the ester solvent include acetic acid ester solvents such as ethyl acetate and n-butyl acetate;
Polyhydric alcohol partial ether carbochelate solvent such as ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate;
Lactone-based solvents such as γ-butyrolactone and valero lactone;
Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate.

Examples of the hydrocarbon solvent include an aliphatic hydrocarbon solvent such as n-hexane;
Examples thereof include aromatic hydrocarbon solvents such as toluene.

Among these, an ester solvent is preferable, a polyhydric alcohol partial ether carboxylate solvent is more preferable, and propylene glycol monomethyl ether acetate is further preferable. The composition (S) may contain one or more of the [B] solvents.

[Other ingredients]
Examples of other components include acid generators or base generators, cross-linking agents, surfactants and the like.

(Acid generator or base generator)
An acid generator is a component that generates an acid by the action of heat or radiation. A base generator is a component that generates a base by the action of heat or radiation. When the composition (S) contains an acid generator or a base generator, the acid or base is generated by irradiation in radiation or heating in a heating step or the like, so that the cross-linking reaction in the polymer [A] or the like is promoted. be able to. The composition (S) may contain one or more acid generators or base generators.

Examples of the acid generator include onium salt compounds, N-sulfonyloxyimide compounds and the like.

Examples of the onium salt compound include a sulfonium salt such as triphenylsulfonium trifluoromethanesulfonate, a tetrahydrothiophenium salt such as 1- (4-n-butoxynaphthalene-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, and diphenyliodonium. Examples thereof include an iodonium salt such as trifluoromethanesulfonate and an ammonium salt such as triethylammonium trifluoromethanesulfonate. Examples of the N-sulfonyloxyimide compound include N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide and the like.

Examples of the base generator include 4- (methylthiobenzoyl) -1-methyl-1-morpholinoetan, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, and 2-benzyl-2-dimethylamino-1. -(4-Molholinophenyl) -butanone, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, 1- (anthraquinone-2-yl) ethylimidazole carboxylate, 2-nitrobenzylcyclohexylcarbamate, [[(2,6-- Dinitrobenzyl) oxy] cyclohexylamine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine, triphenylmethanol, o-carbamoyl hydroxylamide, o-carbamoyloxime, hexaammine cobalt ( III) Tris (triphenylmethylborate) and the like can be mentioned.

When the composition (S) contains an acid generator or a base generator, the lower limit of the content of the acid generator or the base generator is 0.1 part by mass with respect to 100 parts by mass of the [A] polymer. Is preferable, and 1% by mass is more preferable. The upper limit of the content is preferably 20 parts by mass, more preferably 5 parts by mass.

(Crosslinking agent)
The cross-linking agent is a component that forms a cross-linking bond between components such as the [A] polymer by the action of heat or acid, or forms a cross-linked structure by itself. When the composition (S) contains a cross-linking agent, the hardness of the coating film (P) to be formed can be increased, and as a result, the metal-containing layer (Y) can be formed more effectively. The composition (S) may contain one or more cross-linking agents.

Examples of the cross-linking agent include polyfunctional (meth) acrylate compounds such as trimethylpropantri (meth) acrylate, epoxy compounds such as novolak type epoxy resin, and hydroxymethyl group substitutions such as 2-hydroxymethyl-4,6-dimethylphenol. Phenol compound, 4,4'-(1- (4- (1- (4-hydroxy-3,5-bis (methoxymethyl) phenyl) -1-methylethyl) phenyl) ethylidene) bis (2,6-bis) Examples thereof include an alkoxyalkyl group-containing phenol compound such as (methoxymethyl) phenol, a compound having an alkoxyalkylated amino group such as (poly) methylolated melamine, and a random copolymer of acenaphthylene and hydroxymethyl acenaphthylene. ..

When the composition (S) contains a cross-linking agent, the lower limit of the content of the cross-linking agent is preferably 1 part by mass and more preferably 5 parts by mass with respect to 100 parts by mass of the polymer [A]. The upper limit of the content is preferably 100 parts by mass, more preferably 30 parts by mass.

(Surfactant)
The surfactant is a component capable of improving the coatability of the composition (S) on the metal substrate (X).

When the composition (S) contains a surfactant, the upper limit of the content of the surfactant is preferably 10 parts by mass and more preferably 2 parts by mass with respect to 100 parts by mass of the polymer [A]. The lower limit of the content is, for example, 0.1 parts by mass.

[Method for preparing composition]
The composition (S) is, for example, a high-density polyethylene filter obtained by mixing the polymer [A], the solvent [B] and, if necessary, other components in a predetermined ratio, and preferably having pores having a pore size of about 0.45 μm. It can be prepared by filtering with or the like. The lower limit of the solid content concentration of the composition (S) is preferably 0.1% by mass, more preferably 0.5% by mass, and even more preferably 0.7% by mass. The upper limit of the solid content concentration is preferably 30% by mass, more preferably 10% by mass, and even more preferably 3% by mass.

<Metal-containing layer forming process>
In this step, a metal-containing layer (Y) is formed on at least a part of the surface of the coating film (P) formed by the coating step on the side opposite to the metal substrate (X).

Examples of the metal atom (B) contained in the metal-containing layer (Y) include metal atoms exemplified as the metal atom (A) contained in the metal substrate (X) described above. Of these, copper or cobalt is preferred.

Examples of the method for forming the metal-containing layer (Y) include a method of immersing a metal substrate (X) on which a coating film (P) is formed in a liquid containing a metal atom (B), chemical vapor deposition (CVD). Examples thereof include a method of adhering a metal atom (B) to the surface of a coating film (P) formed on a metal substrate (X) by a method or an atomic layer deposition (ALD) method.

Examples of the liquid containing the metal atom (B) used in the above dipping method include an aqueous solution of a metal salt such as copper sulfate and cobalt chloride. The concentration of the metal salt in the aqueous solution of the metal salt is, for example, 0.01 mol / L or more and 3 mol / L or less, preferably 0.1 mol / L or more and 1 mol / L or less. The immersion time is, for example, 1 minute or more and 1 day or less, preferably 1 hour or more and 100 hours or less.

After the immersion, it is preferable to wash and remove the metal atom (B) that is not chemically bonded to the functional group (M) in the coating film (P) with ultrapure water or the like.

Examples of the CVD method include various methods such as thermal CVD, plasma CVD, optical CVD, reduced pressure CVD, and laser CVD organic metal CVD (MOCVD).
Examples of the ALD method include a thermal ALD method and a plasma ALD method.

The lower limit of the average thickness of the formed metal-containing layer (Y) is preferably 0.1 nm, more preferably 1 nm, and even more preferably 2 nm. The upper limit of the average thickness is preferably 500 nm, more preferably 100 nm, and even more preferably 50 nm.

The metal atom (B) contained in the metal-containing layer (Y) is preferably different from the metal atom (A) contained in the metal substrate (X). When the metal atom (B) and the metal atom (A) are different from each other, the metal-containing layer (Y) can be formed more effectively.

When the metal substrate (X) contains a metal atom (A) and the metal-containing layer (Y) contains a metal atom (B) different from the metal atom (A), the terminal structure (I) of the [A] polymer ) Has a functional group capable of chemically bonding with the metal atom (A), and the terminal structure (II) preferably has a functional group capable of chemically bonding with the metal atom (B). When the structures of the metal substrate (X), the metal-containing layer (Y), and the polymer [A] are combined as described above, the metal-containing layer (Y) can be more easily formed on the surface of the metal substrate (X).

In this case, a phosphoric acid group is preferable as the functional group capable of chemically bonding with the metal atom (A). Further, as the functional group capable of chemically bonding with the metal atom (B), at least one selected from the group consisting of a nitrile group, a carboxy group, an ester group and a hydroxy group is preferable. Assuming that the functional group (M) is as described above, the formation of the metal-containing layer (Y) on the surface of the metal substrate (X) is more likely to occur due to the magnitude of the bonding force between each functional group (M) and the metal atom. It can be done effectively.

According to the method for manufacturing the metal substrate, the metal-containing layer (Y) can be easily formed on the surface of the metal substrate (X). In the method for manufacturing the metal substrate, by using a substrate having a trench in which a pattern such as polysiloxane is formed on the surface of a metal substrate such as cobalt or copper as the metal substrate (X), the metal at the bottom of the trench is formed. A metal-containing layer (Y) can be formed on the surface. According to the substrate on which the metal-containing layer (Y) is formed at the bottom of such a trench, it is considered that the growth of the plating layer during the plating treatment is promoted.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. The measurement method of each physical property value is shown below.

[Mw and Mn]
Mw and Mn of the polymer are measured by gel permeation chromatography (GPC) using Tosoh's GPC columns (2 "G2000HXL", 1 "G3000HXL" and 1 "G4000HXL") under the following conditions. bottom.
Eluent: Tetrahydrofuran (Wako Pure Chemical Industries, Ltd.)
Flow rate: 1.0 mL / min Sample concentration: 1.0 mass%
Sample injection volume: 100 μL
Column temperature: 40 ° C
Detector: Differential refractometer Standard material: Monodisperse polystyrene

[ ¹³ C-NMR analysis]
¹³ C-NMR analysis was performed using a nuclear magnetic resonance apparatus (“JNM-EX400” manufactured by JEOL Ltd.) and DMSO-d ₆ as a measurement solvent. The content ratio of each structural unit in the polymer was calculated from the area ratio of the peak corresponding to each structural unit in the spectrum obtained by ^{13 C-NMR.}

<[A] Synthesis of polymer>
[Synthesis Example 1]
Add 0.098 g of azobisisobutyronitrile (AIBN), 10.63 g of styrene, 0.83 g of 2-cyano-2-propyldodecyltrithiocarbonate and 20 g of anisole to a 200 mL three-necked flask reaction vessel, and add a nitrogen atmosphere. Below, the mixture was heated and stirred at 80 ° C. for 5 hours. Next, 0.68 g of vinyl phosphate and 1.0 g of propylene glycol monomethyl ether were added, and the mixture was heated and stirred at 80 ° C. for 3 hours. This polymerization reaction solution was added to 300 g of methanol for precipitation purification, the obtained yellow viscous substance was recovered, dissolved in 20 g of propylene glycol monomethyl ether acetate, 0.49 g of AIBN and 2.03 g of tert-dodecanethiol were added, and the mixture was added. The mixture was stirred at 80 ° C. for 2 hours to carry out a cleavage reaction at the end of trithiocarbonate. The obtained polymerization reaction solution was concentrated under reduced pressure, and the obtained concentrate was added to 1,000 g of methanol for precipitation purification to obtain a pale yellow solid. Then, this solid was dried under reduced pressure at 60 ° C. to obtain 10.5 g of the polymer (A-1). This polymer (A-1) had Mw of 5,600, Mn of 4,800, and Mw / Mn of 1.17.

[Synthesis Example 2]
In a 200 mL three-necked reaction vessel, 0.098 g of AIBN, 0.83 g of 2-cyano-2-propyldodecyltrithiocarbonate, 17.6 g of tert-butylstyrene, 0.78 g of 4-vinylbenzocyclobutene and 20 g of anisole were added. In addition, the mixture was heated and stirred at 80 ° C. for 5 hours in a nitrogen atmosphere. Next, 0.68 g of vinyl phosphate and 1.0 g of propylene glycol monomethyl ether were added, and the mixture was heated and stirred at 80 ° C. for 3 hours. This polymerization reaction solution was added to 300 g of methanol for precipitation and purification, the obtained yellow viscous substance was recovered, dissolved in 20 g of propylene glycol monmethyl ether acetate, and 0.49 g of AIBN and 2.03 g of tert-dodecanethiol were added. , The mixture was stirred at 80 ° C. for 2 hours to carry out a reaction for separating the ends of trithiocarbonate. The obtained polymerization reaction solution was concentrated under reduced pressure, and the obtained concentrate was added to 1,000 g of methanol for precipitation purification to obtain a pale yellow solid. Then, this solid was dried under reduced pressure at 60 ° C. to obtain 14.6 g of the polymer (A-2). This polymer (A-2) had Mw of 6,300, Mn of 4,900, and Mw / Mn of 1.29.

[Synthesis Example 3]
After drying the 500 mL flask reaction vessel under reduced pressure, 120 g of tetrahydrofuran (THF) subjected to distillation dehydration treatment and 9.2 mL of a 0.5 N lithium chloride THF solution were injected under a nitrogen atmosphere, and the mixture was cooled to −78 ° C. Next, 2.38 mL of a 1N cyclohexane solution of sec-butyllithium (sec-BuLi) was injected into this THF solution, and then adsorption filtration with silica gel and distillation dehydration treatment were performed to remove the polymerization inhibitor. .3 mL was added dropwise over 30 minutes, and it was confirmed that the polymerization system was orange. At the time of this dropping injection, care was taken so that the internal temperature of the reaction solution did not exceed -60 ° C. It was aged for 30 minutes after the completion of the dropping. After that, 0.19 mL of 3-bromopropionitrile was injected to carry out a termination reaction at the polymerization terminal. The reaction solution was heated to room temperature, and the obtained reaction solution was concentrated and replaced with methyl isobutyl ketone (MIBK). Then, 1,000 g of a 2% by mass aqueous solution of oxalic acid was injected and stirred, allowed to stand, and then the lower aqueous layer was removed. This operation was repeated 3 times to remove the Li salt. Then, 1,000 g of ultrapure water was injected and stirred to remove the lower aqueous layer. This operation was repeated 3 times to remove oxalic acid, then the solution was concentrated and added dropwise to 500 g of methanol to precipitate a polymer, and the solid was recovered with a Buchner funnel. This solid was dried under reduced pressure at 60 ° C. to obtain 11.9 g of a white polymer (A-3). This polymer (A-3) had Mw of 5,600, Mn of 5,200, and Mw / Mn of 1.08.

<Preparation of composition (S)>
[Preparation Example 1]
To 1.20 g of (A-1) as a polymer of [A], 98.80 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent of [B] was added, and after stirring, a high density having 0.45 μm pores was added. The composition (S-1) was prepared by filtering with a density polyethylene filter.

[Preparation Example 2 and Comparative Preparation Example 1]
The compositions (S-2) and (S-3) were prepared in the same manner as in Preparation Example 1 above, except that each component of the type and the blending amount shown in Table 1 below was used.

<Manufacturing of substrate>
[Examples 1 and 2 and Comparative Example 1]
[Coating of composition]
The 8-inch cobalt substrate was immersed in a 5% by mass aqueous solution of oxalic acid and then dried by a nitrogen flow to remove an oxide film on the surface. Further, the same treatment was performed on the copper substrate. The silicon oxide (SiO ₂ ) substrate was surface-treated with isopropanol.
Next, using a truck (“TELDSA ACT8” manufactured by Tokyo Electron Limited), the composition (S) shown in Table 2 below was spin-coated at 1,500 rpm and baked at 100 ° C. for 180 seconds.

The contact angle value of water on the surface of the substrate coated with the obtained composition (S) was measured using a contact angle meter (“Drop master DM-501” manufactured by Kyowa Surface Chemistry Co., Ltd.). The measured values of the contact angle are shown in Table 2 below.

[Coating of composition and formation of metal-containing layer]
[Examples 1 and 2 and Comparative Example 1]
A cobalt substrate and a copper substrate are cut into a coupon shape of 3 cm × 3 cm, and the composition (S) shown in Tables 3 and 4 below is spin-coated on the surface of each substrate at 1,500 rpm and at 100 ° C. for 180 seconds. It was fired. Next, the [A] polymer that was not chemically bonded to the surface of the metal substrate was removed by PGMEA and dried by nitrogen blowing.
Next, the obtained cobalt substrate was immersed in a 1 M copper sulfate aqueous solution and the obtained copper substrate in a 1 M cobalt chloride aqueous solution for 72 hours in a chalet containing 20 g of each metal salt aqueous solution, and then the [A] polymer was used. Copper sulfate or cobalt chloride which was not chemically bonded to the above was removed with ultrapure water and dried with a nitrogen blow.

The surface of each of the obtained substrates was analyzed by a scanning X-ray photoelectron spectrometer (“Quantum2000” manufactured by ULVAC-PHI) (measurement conditions: 100 μmφ), and the qualitative and quantification of each element was performed. The evaluation results are shown in Tables 3 and 4. The "others" in the ESCA (XPS) surface data include baresi, thermal oxide, TiN, Ti, N, Si and the like on the Co multilayer.

From the results in Table 3, it can be seen that the Cu component was detected in the cobalt substrate obtained by applying the composition (S) to the cobalt substrate and immersing and adsorbing it in a 1 M copper sulfate aqueous solution. It can be seen that the Co component was detected in the mixture obtained by applying the composition (S) and immersing and adsorbing it in a 1 M aqueous cobalt chloride solution. As described above, according to the method for manufacturing a substrate of the example, it is possible to easily manufacture a substrate in which a metal-containing layer is formed on the surface of the metal substrate.

According to the method for manufacturing a substrate of the present invention, it is possible to easily manufacture a substrate having a metal-containing layer formed on the surface of the metal substrate. The composition of the present invention can be suitably used in the method for producing the substrate. The polymer of the present invention can be suitably used as a polymer component of the composition. Therefore, these can be suitably used for processing processes of semiconductor devices, which are expected to be further miniaturized in the future.

Claims (9)

The process of applying the composition on a metal substrate and
A method for manufacturing a substrate, which comprises a step of forming a metal-containing layer on at least a part of a coating film formed by the coating step.
The composition contains a polymer having a first-terminal structure and a second-terminal structure on the same molecule, and a solvent.
The first terminal structure and the second terminal structure are at least one selected from the group consisting of the structure represented by the following formula (1) and the structure represented by the following formula (2), respectively. Substrate manufacturing method.

(In the formula (1), L ¹ is a trivalent group having 1 to 20 carbon atoms. A ¹ is a monovalent group containing a functional group that can be chemically bonded to a metal atom. X is hydrogen. atom, a monovalent organic group having 1 to 20 carbon atoms, ^{.A 11} is -SH or ^{-S-a 11} is a monovalent group containing a metal atom capable of chemically bonding functional groups .n is ^{(-L 1 (-A 1) -} ). represented by _n indicates the number of the structural units constituting the block, which is an integer of 2 or more the plurality of ^{a 1} good .A ¹ and be the same or different A ¹¹ may be the same or different. * Indicates a site of the polymer that binds to a portion other than the structure represented by the above formula (1).
Wherein ^{(2), L} 2 is, -S -, - NR- or ^{-NA 22} - a. A ² and A ²² are monovalent groups each independently containing a functional group capable of chemically bonding with a metal atom. R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. m is 0 or 1. * Indicates a site that binds to a portion of the polymer other than the structure represented by the above formula (2). ) The substrate according to claim 1, wherein the functional group chemically bonded to the metal atom in the first terminal structure of the polymer and the functional group chemically bonded to the metal atom in the second terminal structure are different from each other. Production method. The substrate according to claim 1 or 2, wherein the first terminal structure in the polymer is a structure represented by the above formula (1), and the second terminal structure is a structure represented by the above formula (2). Manufacturing method. ^{Claim 1, in which A 1} in the above formula (1) is a phosphoric acid group, and A ² in the above formula (2) is at least one selected from the group consisting of a nitrile group, a carboxy group, an ester group and a hydroxy group. The method for manufacturing a substrate according to claim 2 or 3. The method for producing a substrate according to any one of claims 1 to 4, wherein the polymer has a structural unit derived from hydrocarbon group-substituted or unsubstituted styrene. The metal substrate contains a first metal atom, and the metal-containing layer contains a second metal atom different from the first metal atom.
A claim that the functional group of the first terminal structure in the polymer can be chemically bonded to the first metal atom, and the functional group of the second terminal structure can be chemically bonded to the second metal atom. The method for manufacturing a substrate according to any one of claims 1 to 5. 6. The functional group of the first terminal structure is a phosphoric acid group, and the functional group of the second terminal structure is at least one selected from the group consisting of a nitrile group, a carboxy group, an ester group and a hydroxy group. The method for manufacturing a substrate according to. A composition used in a method for manufacturing a substrate including a metal substrate and a metal-containing layer formed on the metal substrate.
A polymer having a first-terminal structure and a second-terminal structure on the same molecule and a solvent are contained.
The first terminal structure and the second terminal structure are at least one selected from the group consisting of the structure represented by the following formula (1) and the structure represented by the following formula (2), respectively. Composition.

(In the formula (1), L ¹ is a trivalent group having 1 to 20 carbon atoms. A ¹ is a monovalent group containing a functional group that can be chemically bonded to a metal atom. X is hydrogen. atom, a monovalent organic group having 1 to 20 carbon atoms, ^{.A 11} is -SH or ^{-S-a 11} is a monovalent group containing a metal atom capable of chemically bonding functional groups .n is ^{(-L 1 (-A 1) -} ). represented by _n indicates the number of the structural units constituting the block, which is an integer of 2 or more the plurality of ^{a 1} good .A ¹ and be the same or different A ¹¹ may be the same or different. * Indicates a site of the polymer that binds to a portion other than the structure represented by the above formula (1).
Wherein ^{(2), L} 2 is, -S -, - NR- or ^{-NA 22} - a. A ² and A ²² are monovalent groups each independently containing a functional group capable of chemically bonding with a metal atom. R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. m is 0 or 1. * Indicates a site that binds to a portion of the polymer other than the structure represented by the above formula (2). ) It has a first terminal structure and a second terminal structure on the same molecule, and the first terminal structure and the second terminal structure are represented by the following formula (1) and the following formula (2), respectively. A polymer that is at least one selected from the group consisting of.

(In the formula (1), L ¹ is a trivalent group having 1 to 20 carbon atoms. A ¹ is a monovalent group containing a functional group that can be chemically bonded to a metal atom. X is hydrogen. atom, a monovalent organic group having 1 to 20 carbon atoms, ^{.A 11} is -SH or ^{-S-a 11} is a monovalent group containing a metal atom capable of chemically bonding functional groups .n is ^{(-L 1 (-A 1) -} ). represented by _n indicates the number of the structural units constituting the block, which is an integer of 2 or more the plurality of ^{a 1} good .A ¹ and be the same or different A ¹¹ may be the same or different. * Indicates a site of the polymer that binds to a portion other than the structure represented by the above formula (1).
Wherein ^{(2), L} 2 is, -S -, - NR- or ^{-NA 22} - a. A ² and A ²² are monovalent groups each independently containing a functional group capable of chemically bonding with a metal atom. R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. m is 0 or 1. * Indicates a site that binds to a portion of the polymer other than the structure represented by the above formula (2). )